EP3002303A1 - New phenolic polymers and preparation processes thereof - Google Patents

New phenolic polymers and preparation processes thereof Download PDF

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Publication number
EP3002303A1
EP3002303A1 EP14306563.9A EP14306563A EP3002303A1 EP 3002303 A1 EP3002303 A1 EP 3002303A1 EP 14306563 A EP14306563 A EP 14306563A EP 3002303 A1 EP3002303 A1 EP 3002303A1
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Prior art keywords
group
radical
formula
compound
alkyl group
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EP14306563.9A
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German (de)
French (fr)
Inventor
Stéphane GRELIER
Henri Cramail
Audrey Llevot
Stéphane CARLOTTI
Etienne GRAU
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Centre National de la Recherche Scientifique CNRS
Universite de Bordeaux
Institut Polytechnique de Bordeaux
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Centre National de la Recherche Scientifique CNRS
Universite de Bordeaux
Institut Polytechnique de Bordeaux
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Priority to EP14306563.9A priority Critical patent/EP3002303A1/en
Priority to CA2963310A priority patent/CA2963310C/en
Priority to PCT/EP2015/072958 priority patent/WO2016050989A1/en
Priority to EP15771994.9A priority patent/EP3201251B1/en
Priority to US15/516,359 priority patent/US10053540B2/en
Publication of EP3002303A1 publication Critical patent/EP3002303A1/en
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    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
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    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
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    • C08G63/66—Polyesters containing oxygen in the form of ether groups
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
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Definitions

  • the present invention concerns the use of specific phenolic monomers for the preparation of polymers.
  • the present invention also relates to new phenolic polymers, in particular polyesters, polyamides, epoxy resins and unsaturated polyesters, and preparation processes thereof.
  • Aromatic compounds constitute basic chemicals to manufacture everyday life items. Indeed, they play a key role in pharmaceutical, perfumes, dyestuff and polymer industries. In plastic industry, aromatic units offer rigidity, hydrophobicity and fire resistance to the derived polymers. Aromatic polyesters, such as polyalkyleneterephtalate are widely commercially used, especially in food packaging and textile field due to their good thermomechanical properties. Aromatic polyamides, such as Kevlar constitute high performance polymers thanks to their high stability and rigidity. Finally, phenolic compounds constitute a widely used raw material. For instance, Bisphenol A is an important monomer for the synthesis of polycarbonates, epoxy resins and a popular plasticizer for thermoplastic polymers. These compounds are mainly petroleum based and derived from benzene, xylene and toluene.
  • Phenolic polymers are difficult to prepare as it is not easy to prepare appropriate monomers with a sufficient purity.
  • the high purity of the monomers is a pre-requisite to the synthesis of high molar mass polymer.
  • the present invention relates to the use of a compound having the following formula (I): wherein:
  • the repetitive unit U as defined above may comprise other moieties or other functional group(s) linked to the moiety of formula (III).
  • the compound of formula (IV) is a polymer which possesses n units U having the formula (U-1), which comprise the moiety of formula (III-1): wherein R 2 and R 6 are as defined above.
  • the bond wherein the sign is present means that said bond is linked to another moiety, for example another functional group.
  • the polymer having the following formula (IV) may be written as follows:
  • a 1 is a (C 2 -C 10 )alkylene radical, more particularly an octylene radical or an ethylene radical.
  • a 1 is a (C 3 -C 12 )cycloalkylene radical, optionally substituted by at least one (C 1 -C 10 )alkyl group.
  • a 1 is a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C 1 -C 10 )alkyl group.
  • a 1 represents:
  • a 1 is a radical of formula -B 1 -B 2 -B 3 - wherein:
  • a 1 is:
  • a 1 is a radical of formula -B 4 -B 5 -, wherein B 4 and B 5 , identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C 1 -C 6 )alkoxy groups.
  • a 1 is:
  • the present invention also concerns a process for preparing a compound having formula (IV) or (IV-1), said process comprising at least one step of polymerization of:
  • the polymerization step is carried out at a temperature comprised between 80°C and 250°C, preferably between 120°C and 200°C.
  • the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is Ti(OBu) 4 , and is used at 0.5% molar.
  • the compound of formula (V) has the following formula (V-1): HOOC-A 1 -COOH (V-1) wherein A 1 is as defined above.
  • the compound of formula (V) has the following formula (V-2): R b OOC-A 1 -COOR b (V-2) wherein A 1 is as defined above, and R b is a (C 1 -C 6 )alkyl group.
  • the repetitive unit U has the following formula (U-2): wherein OR 6 corresponds to the R 1 group of the moiety of formula (III), A 4 , R 6 and R 2 being as defined above.
  • R 2 is a methoxy group.
  • R 6 is a methyl group.
  • a 4 represents a decylene radical.
  • the compound having the following formula (I-2) has the following formula (I-2-1):
  • the compound of formula (I-2-1) corresponds to a compound of formula (I-2) wherein R 2 is methoxy and R 6 is methyl.
  • the repetitive unit U has the following formula (U-3): wherein OR 6 corresponds to the R 1 group of the moiety of formula (III), A 2 , R 6 and R 2 being as defined above.
  • R 2 is a methoxy group.
  • the polymer of formula (VI-1) corresponds to a polymer of formula (VI) wherein R 2 is methoxy and R 6 is methyl.
  • a 2 is a radical of formula -B' 1 -B' 2 -B' 3 - wherein:
  • a 2 is:
  • the present invention also relates to a process for preparing a polymer having the formulae (VI) or (VI-1) as defined above, comprising at least one step of polymerization of:
  • the compound of formula (VII-1) is chosen from the following compounds:
  • a preferred diamine of formula (X) has the following formula:
  • R 6 is a methyl group.
  • the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is used at 2% molar.
  • R' 7 is a (C 1 -C 10 )alkyl group, in particular a methyl group.
  • (C x -C y )alkylene refers to a divalent saturated aliphatic hydrocarbon radical, comprising from x to y carbon atoms, having preferably from 1 to 20, in particular 1 to 12 carbon atoms, and more preferably 2 to 10 carbon atoms.
  • said radical When said radical is linear, it may be represented by the formula (CH 2 ) m wherein m is an integer varying from 1 to 12, and preferably from 2 to 10.
  • alkylene may be cited as example: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene.
  • arylene refers to a radical derived from arene wherein two hydrogen atoms from the cycle have been deleted.
  • the phenylene radical may be cited.
  • cycloalkylene refers to a divalent, saturated or partially unsaturated, non-aromatic monocyclic, bicyclic ring system having in particular from 3 to 12 carbon atoms, such as cyclobutylene, cyclopentylene, cyclohexylene.
  • Methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 160 °C for 2 h under nitrogen flow and at 200 °C under vaccum for 6 h in the presence of 2 mol% of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol% of titanium butoxide.
  • catalyst titanium butoxide, zinc acetate or dibutyltin oxide
  • DSC Differential Scanning Calorimetry
  • TGA Thermogravimetric analyses

Abstract

The present invention concerns the use of a compound having the following formula (I):
Figure imga0001
 for the preparation of a polymer.
The present invention also concerns the polymers obtained from the polymerization of compound of formula (I), and their processes of preparation.

Description

  • The present invention concerns the use of specific phenolic monomers for the preparation of polymers.
  • The present invention also relates to new phenolic polymers, in particular polyesters, polyamides, epoxy resins and unsaturated polyesters, and preparation processes thereof.
  • Aromatic compounds constitute basic chemicals to manufacture everyday life items. Indeed, they play a key role in pharmaceutical, perfumes, dyestuff and polymer industries. In plastic industry, aromatic units offer rigidity, hydrophobicity and fire resistance to the derived polymers. Aromatic polyesters, such as polyalkyleneterephtalate are widely commercially used, especially in food packaging and textile field due to their good thermomechanical properties. Aromatic polyamides, such as Kevlar constitute high performance polymers thanks to their high stability and rigidity. Finally, phenolic compounds constitute a widely used raw material. For instance, Bisphenol A is an important monomer for the synthesis of polycarbonates, epoxy resins and a popular plasticizer for thermoplastic polymers. These compounds are mainly petroleum based and derived from benzene, xylene and toluene.
  • Phenolic polymers are difficult to prepare as it is not easy to prepare appropriate monomers with a sufficient purity. The high purity of the monomers is a pre-requisite to the synthesis of high molar mass polymer.
  • The aim of the present invention is to provide new phenolic thermoplastic polymers for use in numerous applications, as fibers, films, foams, composites, adhesives, coatings, etc... The latter exhibit high thermal stability, high glass transition temperature and high mechanical properties. In addition, the presence of remaining phenolic functions onto the polymer skeleton also brings other properties to these materials such as anti-bacterial activity.
  • The present invention relates to the use of a compound having the following formula (I):
    Figure imgb0001
     wherein:
    • R1 is H or a OR7 group, R7 being H, a (C1-C10)alkyl group or a (C2-C6)alkenyl group;
    • R2 is a (C1-C6)alkoxy group;
    • R3 is H or a radical of formula (II)
      Figure imgb0002
       k being an integer varying from 1 to 6;
    • R4 is a (C1-C6)alkoxy group or a radical X chosen from the group consisting of: (C2-C6)alkenyl groups, (C1-C10)alkyl group, -COOH, -CH2OH, and -COORa, Ra being a (C1-C6)alkyl group or a (C2-C12)alkenyl group;
      and wherein:
    • when R1 is H, then R3 is a group of formula (II) and R4 is a (C1-C6)alkoxy group, and
    • when R1 is a OR7 group, then R3 is H and R4 is X as defined above, for the preparation of a polymer.
  • The present invention is based on the fact that the compounds of formula (I) may be used as monomers suitable to be used for subsequent polymerization.
  • In one embodiment, the compound of formula (I) has one of the following formulae (I-1), (I-2), (I-3), (I-4) or (I-5):
    Figure imgb0003
    Figure imgb0004
    Figure imgb0005
    Figure imgb0006
     wherein:
    • R2 and k are as defined above in formula (I),
    • R' is a (C1-C6)alkoxy group;
    • R6 is a (C1-C6)alkyl group;
    • R'7 is chosen from the group consisting of: (C1-C10)alkyl groups and (C2-C6)alkenyl groups, and
    • Rg is chosen from the group consisting of: (C1-C10)alkyl groups, (C2-C6)alkenyl groups, and -COORa groups, Ra being a (C2-C12)alkenyl group, wherein, when R'7 is an alkyl group, then Rg is chosen from the (C2-C6)alkenyl groups and -COORa groups, and when R'7 is an alkenyl group, then Rg is an alkyl group.
  • The present invention also relates to a polymer susceptible to be obtained by polymerization of the compound of formula (I) as defined above. Such polymer is obtained by implementing a polymerization step according to the polymerization methods well-known in the art of the compound of formula (I) as defined above.
  • The present invention also relates to a polymer susceptible to be obtained by polymerization of the compound of formula (I) as defined above, and of a monomer chosen from the group consisting of: diacids, diesters, diamines, and epoxy compounds.
  • In one embodiment, the diacids and the diesters are selected from the compounds having the following formula (V):

             RbOOC-A1-COORb     (V)

    wherein:
    • Rb is H or (C1-C6)alkyl group; and
    • A1 is chosen from the group consisting of:
      • o a (C2-C10)alkylene radical;
      • o a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group;
      • o a (C2-C30)alkenylene radical;
      • o an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;
      • o a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group; and
      • o a radical of formula -B1-B2-B3- wherein:
        • B2 is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, and
        • B1 and B3, identical or different, are chosen from the (C2-C15)alkylene radicals;
      • o a radical of formula -B4-B5-, wherein B4 and B5, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C1-C6)alkoxy groups.
  • In one embodiment, the diamines are selected from the compounds having the following formula (VII):

             H2N-A2-NH2     (VII)

    wherein A2 is chosen from the group consisting of:
    • o a (C2-C10)alkylene radical;
    • o a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group;
    • o a (C2-C30)alkenylene radical;
    • o an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;
    • o a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group; and
    • o a radical of formula -B'1-B'2-B'3- wherein:
      • B'2 is a (C1-C10)alkylene radical, and
      • B'1 and B'3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;
  • In another embodiment, the diamines are selected from the compounds having the following formula (X):

             H2N-A3-NH2     (X)

    wherein A3 is a radical of formula -B",-B"2- wherein:
    • B"1 is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, and
    • B"2 is a (C1-C10)alkylene radical.
  • The present invention also relates to a polymer susceptible to be obtained by polymerization of the compound of formula (I) as defined above, comprising at least one repetitive unit U, said unit U comprising a moiety having the following formula (III):
    Figure imgb0007
     wherein:
    • R1 represents OR7 group, R7 being H or a (C1-C10)alkyl group; and
    • R2 represents a (C1-C6)alkoxy group.
  • The repetitive unit U as defined above may comprise other moieties or other functional group(s) linked to the moiety of formula (III).
  • In one embodiment, in the formula (III) above-mentioned, R1 and R2, identical or different, are chosen from the (C1-C6)alkoxy groups. In particular, R1 and R2 represent a methoxy group.
  • In one embodiment, the present invention relates to a polymer as defined above comprising at least one repetitive unit U, wherein said unit U comprises a moiety having the formula (III-a):
    Figure imgb0008
  • In one embodiment, the present invention relates to a polymer as defined above comprising at least one repetitive unit U, wherein said unit U comprises a moiety having the formula (III-b):
    Figure imgb0009
  • The present invention also relates to a compound having the following formula (IV):
    Figure imgb0010
     wherein:
    • A1 is as defined above in formula (V);
    • R2 is a (C1-C6)alkoxy group;
    • R6 is a (C1-C6)alkyl group; and
    • n is an integer varying from 1 to 130.
  • According to a preferred embodiment, in formula (IV), n is greater than 2, preferably greater than 5, and in particular greater than 10.
  • The compounds of formula (IV) are compounds which are susceptible to be obtained by polymerization of a compound of formula (I) and a diacid or a diester.
  • In the compound having the formula (IV) as defined above, the repetitive unit U has the following formula (U-1):
    Figure imgb0011
     wherein OR6 corresponds to the R1 group of the moiety of formula (III), and A1, R6 and R2 are as defined above.
  • In this compound, the repetitive units U comprise the moiety of formula (III) as defined above, which is linked on one side to a methylene radical and on the other side to a -CH2-O-C(O)-A1-C(O)-O- radical.
  • The compound of formula (IV) is a polymer which possesses n units U having the formula (U-1), which comprise the moiety of formula (III-1):
    Figure imgb0012
     wherein R2 and R6 are as defined above.
  • As used herein, the bond wherein the sign
    Figure imgb0013
     is present, means that said bond is linked to another moiety, for example another functional group. For example, the polymer having the following formula (IV) may be written as follows:
    Figure imgb0014
  • In one embodiment, in formula (IV), R2 is a methoxy group.
  • In one embodiment, in formula (IV), R6 is a methyl group.
  • In one embodiment, the present invention concerns a compound having the following formula (IV-1):
    Figure imgb0015
     wherein A1 and n are as defined above.
  • In one embodiment, in formulae (IV) and (IV-1), A1 is a (C2-C10)alkylene radical, more particularly an octylene radical or an ethylene radical.
  • In one embodiment, in formulae (IV) and (IV-1), A1 is a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group.
  • In one embodiment, in formulae (IV) and (IV-1), A1 is a (C2-C30)alkenylene radical. In particular, A1 represents -(CH2)9-CH=CH-(CH2)9- or -CH=CH-.
  • In one embodiment, in formulae (IV) and (IV-1), A1 is an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group. In particular, A1 represents a phenylene radical.
  • In one embodiment, in formulae (IV) and (IV-1), A1 is a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group. In particular, A1 represents:
    Figure imgb0016
     In one embodiment, in formulae (IV) and (IV-1), A1 is a radical of formula -B1-B2-B3- wherein:
    • B2 is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is substituted by at least one (C1-C10)alkyl group, and
    • B1 and B3, identical or different, are chosen from the (C8-C12)alkylene radicals.
  • In particular, A1 is:
    Figure imgb0017
  • In one embodiment, in formulae (IV) and (IV-1), A1 is a radical of formula -B4-B5-, wherein B4 and B5, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C1-C6)alkoxy groups.
  • In particular, A1 is:
    Figure imgb0018
  • In one embodiment, in formulae (IV) and (IV-1), n is an integer varying from 2 to 130. According to a preferred embodiment, in formula (IV) or (IV-1), n is greater than 5, and in particular greater than 10.
  • The present invention also concerns a process for preparing a compound having formula (IV) or (IV-1), said process comprising at least one step of polymerization of:
    • a compound having the following formula (I-1):
      Figure imgb0019
       wherein R2 and R6 are as defined above,
    • and a compound of formula (V) as defined above.
  • In one embodiment, the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu)4, dibutyl tin oxide (DBTO), and mixtures thereof.
  • In one embodiment, the polymerization step is carried out at a temperature comprised between 80°C and 250°C, preferably between 120°C and 200°C.
  • Typically, the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is Ti(OBu)4, and is used at 0.5% molar.
  • In one embodiment, the compound having the following formula (I-1) has the following formula (I-1-1):
    Figure imgb0020
  • In another embodiment, the compound of formula (V) has the following formula (V-1):

             HOOC-A1-COOH     (V-1)

    wherein A1 is as defined above.
  • In another embodiment, the compound of formula (V) has the following formula (V-2):

             RbOOC-A1-COORb     (V-2)

    wherein A1 is as defined above, and Rb is a (C1-C6)alkyl group.
  • In one embodiment, preferred compounds of formula (V-1) are chosen from the following compounds:
    Figure imgb0021
    Figure imgb0022
    Figure imgb0023
    Figure imgb0024
    Figure imgb0025
  • In one embodiment, preferred compounds of formula (V-2) are chosen from the following compounds:
    Figure imgb0026
    Figure imgb0027
    Figure imgb0028
  • The present invention also relates to a compound having the following formula (IV-bis):
    Figure imgb0029
     wherein:
    • A4 is a (C2-C10)alkylene radical;
    • R2 is a (C1-C6)alkoxy group;
    • R6 is a (C1-C6)alkyl group; and
    • n is an integer varying from 1 to 40.
  • According to a preferred embodiment, in formula (IV-bis), n is greater than 2, preferably greater than 5, and in particular greater than 10.
  • The compounds of formula (IV-bis) are polymers which are susceptible to be obtained by polymerization of a compound of formula (I) and a diol.
  • In the compound having the formula (IV-bis) as defined above, the repetitive unit U has the following formula (U-2):
    Figure imgb0030
     wherein OR6 corresponds to the R1 group of the moiety of formula (III), A4, R6 and R2 being as defined above.
  • According to the invention, the compound of formula (IV-bis) is a polymer which possesses n units U having the formula (U-2), which comprise the moiety of formula (III-1):
    Figure imgb0031
     wherein R2 and R6 are as defined above.
  • In one embodiment, in formula (IV-bis), R2 is a methoxy group.
  • In one embodiment, in formula (IV-bis), R6 is a methyl group.
  • In one embodiment, the present invention relates to a compound having the following formula (IV-bis-1):
    Figure imgb0032
     wherein A4 and n are as defined above.
  • The compound of formula (IV-bis-1) corresponds to a polymer of formula (IV-bis) wherein: R2 is methoxy and R6 is methyl.
  • In one embodiment, in formulae (IV-bis) and (IV-bis-1), A4 represents a decylene radical.
  • The present invention also concerns a process for preparing a compound having the formula (IV-bis) or (IV-bis-1) as defined above, comprising at least one step of polymerization of:
    • a compound having the following formula (I-2):
      Figure imgb0033
       wherein R2 and R6 are as defined above,
    • and a compound of formula (VIII):

               HO-A4-OH     (VIII)

      wherein A4 is as defined above.
  • In one embodiment, the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu)4, dibutyl tin oxide (DBTO), and mixtures thereof.
  • In one embodiment, the polymerization step is carried out at a temperature comprised between 80°C and 250°C, preferably between 120°C and 200°C.
  • Typically, the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is Ti(OBu)4, and is used at 0.5% molar.
  • In one embodiment, the compound having the following formula (I-2) has the following formula (I-2-1):
    Figure imgb0034
  • The compound of formula (I-2-1) corresponds to a compound of formula (I-2) wherein R2 is methoxy and R6 is methyl.
  • In another embodiment, the compound of formula (VIII) is:
    Figure imgb0035
  • The present invention also relates to a compound having the following formula (VI):
    Figure imgb0036
     wherein:
    • A2 is as defined above in formula (VII);
    • R2 is a (C1-C6)alkoxy group;
    • R6 is a (C1-C6)alkyl group; and
    • n is an integer varying from 1 to 100.
  • According to a preferred embodiment, in formula (VI), n is greater than 2, preferably greater than 5, and in particular greater than 10.
  • The compounds of formula (VI) are polymers which are susceptible to be obtained by polymerization of a compound of formula (I) and a diamine.
  • In the polymer having the formula (VI) as defined above, the repetitive unit U has the following formula (U-3):
    Figure imgb0037
     wherein OR6 corresponds to the R1 group of the moiety of formula (III), A2, R6 and R2 being as defined above.
  • According to the invention, the polymer of formula (VI) possesses n units U having the formula (U-3), which comprise the moiety of formula (III-1):
    Figure imgb0038
     wherein R2 and R6 are as defined above.
  • In one embodiment, in formula (VI), R2 is a methoxy group.
  • In one embodiment, in formula (VI), R6 is a methyl group.
  • In one embodiment, the present invention relates to a polymer having the following formula (VI-1):
    Figure imgb0039
     wherein A2 and n are as defined above.
  • The polymer of formula (VI-1) corresponds to a polymer of formula (VI) wherein R2 is methoxy and R6 is methyl.
  • In one embodiment, in formulae (VI) and (VI-1), A2 is a (C2-C10)alkylene radical, more particularly a hexylene radical or a decylene radical.
  • In one embodiment, in formulae (VI) and (VI-1), A2 is a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group.
  • In one embodiment, in formulae (VI) and (VI-1), A2 is a (C2-C30)alkenylene radical.
  • In one embodiment, in formulae (VI) and (VI-1), A2 is an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group, in particular a phenylene.
  • In one embodiment, in formulae (VI) and (VI-1), A2 is a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group.
  • In one embodiment, in formulae (VI) and (VI-1), A2 is a radical of formula -B'1-B'2-B'3- wherein:
    • B'2 is a (C1-C10)alkylene radical, and
    • B'1 and B'3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group.
  • In particular, A2 is:
    Figure imgb0040
  • The present invention also relates to a process for preparing a polymer having the formulae (VI) or (VI-1) as defined above, comprising at least one step of polymerization of:
    • a compound having the following formula (I-3):
      Figure imgb0041
       wherein R2 and R6 are as defined above,
    • and a diamine of formula (VII) H2N-A2-NH2, A2 being as defined above.
  • In one embodiment, the polymerization step is carried out at a temperature comprised between 60 °C and 250 °C, preferably between 80 °C and 240 °C.
  • In one embodiment, the polymerization step is carried out in presence of an equimolar quantity of the compounds of formula (I-3) and the diamine of formula (VII).
  • In one embodiment, the compound having the following formula (I-3), used in the above-mentioned process, has the following formula (I-3-1):
    Figure imgb0042
  • In another embodiment, the compound of formula (VII) has the following formula (VII-1):

             H2N-(CH2)p-NH2     (VII-1)

    wherein p is an integer comprised from 1 to 20, preferably from 2 to 12.
  • In an embodiment, the compound of formula (VII-1) is chosen from the following compounds:
    Figure imgb0043
    Figure imgb0044
  • In another embodiment, the compound of formula (VII) has the following formula (VII-2):
    Figure imgb0045
     wherein q is an integer comprised from 1 to 20, preferably from 1 to 10. In one embodiment, the compound of formula (VII-2) is as follows:
    Figure imgb0046
  • The present invention also relates to a polymer having a repetitive unit comprising a moiety having the following formula (IX):
    Figure imgb0047
     wherein:
    • R2 is as defined above,
    • k is an integer varying from 1 to 6,
    • R' is a (C1-C6)alkoxy group, and
    • A3 is as defined above in formula (X).
  • The present invention also relates to the process for preparing a polymer comprising repetitive units containing a moiety having the formula (IX) as defined above, comprising at least one step of polymerization of:
    • a compound having the following formula (I-4):
      Figure imgb0048
       wherein:
      • . R2 is as defined above,
      • . k is an integer varying from 1 to 6,
      • . R' is a (C1-C6)alkoxy group;
    • and a diamine of formula (X) H2N-A3-NH2, A3 being as defined above,
  • A3 being preferably a radical of formula -B"1-B"2- wherein:
    • B"1 is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, and
    • B"2 is a (C1-C10)alkylene radical.
  • In one embodiment, the polymerization step is carried out at a temperature comprised between 60 °C and 250 °C, preferably between 80 °C and 200 °C.
  • In the process of the invention, a preferred compound of formula (I-4) has the following formula (I-4-1):
    Figure imgb0049
     k being a defined above, such as for example the following compound:
    Figure imgb0050
  • In the process of the invention, a preferred diamine of formula (X) has the following formula:
    Figure imgb0051
  • The present invention also relates to a compound having the following formula (XI-A) or (XI-B):
    Figure imgb0052
     wherein:
    • R2 is a (C1-C6)alkoxy group;
    • R6 is a (C1-C10)alkyl group,
    • Y is chosen from the group consisting of: a bond, a (C1-C10)alkylene group,-C(O)O-Rc- and -Rc-O(O)C, Rc being a (C1-C10)alkylene radical;
    • R8 is a (C1-C6)alkoxy group or a (C1-C10)alkyl group; and
    • n is an integer varying from 10 to 120.
  • In the compound having the formula (XI-A) as defined above, the repetitive unit U has the following formula (U-4):
    Figure imgb0053
     wherein OR6 corresponds to the R1 group of the moiety of formula (III), Y and R2 being as defined above.
  • According to the invention, the compound of formula (XI-A) is a polymer which possesses n units U having the formula (U-4), which comprise the moiety of formula (III-1) as defined above.
  • In one embodiment, in formulae (XI-A) and (XI-B), R2 is a methoxy group.
  • In one embodiment, in formulae (XI-A) and (XI-B), R6 is a methyl group.
  • In one embodiment, in formulae (XI-A) and (XI-B), R8 is a (C1-C6)alkoxy group, in particular a methoxy group.
  • In one embodiment, in formulae (XI-A) and (XI-B), R8 is a (C1-C10)alkyl group, in particular a methyl group.
  • In one embodiment, the present invention relates to a polymer having the following formula (XI-A-1) or (XI-B-1):
    Figure imgb0054
    Figure imgb0055
     wherein Y, R8 and n are as defined above.
  • In one embodiment, in formulae (XI-A) and (XI-A-1), Y is a bond.
  • In one embodiment, in formulae (XI-A) and (XI-A-1), Y is a (C1-C10)alkylene group, in particular a methylene group.
  • In one embodiment, in formulae (XI-A) and (XI-A-1), Y is a radical -COORc- or -RcOOC-, Rc being as defined above and being in particular a nonylene radical.
  • In one embodiment, in formulae (XI-B) and (XI-B-1), R8 is a (C1-C10)alkyl group, in particular a methyl group.
  • The present invention also relates to a process for preparing a compound having the formulae (XI-A) or (XI-B), comprising at least one step of polymerization of a compound having the following formula (I-5):
    Figure imgb0056
     wherein:
    • R2 is as defined above;
    • R'7 is chosen from the group consisting of: (C1-C10)alkyl groups and (C2-C6)alkenyl groups, and
    • Rg is chosen from the group consisting of: (C1-C10)alkyl groups, (C2-C6)alkenyl groups, and -COORa groups, Ra being a (C2-C12)alkenyl group, wherein, when R'7 is an alkyl group, then Rg is chosen from the (C2-C6)alkenyl groups and -COORa groups, and when R'7 is an alkenyl group, then Rg is an alkyl group.
  • In one embodiment, the polymerization step is carried out in the presence of a Grubbs catalyst. These Grubbs catalysts are a series of transition metal carbene complexes used in particular as catalysts for olefin metathesis. The main advantage of these catalysts is their compatibility with different functional groups. The activity of these catalysts in acyclic diene metathesis polymerization (ADMET) has been widely demonstrated in a large number of publications. Such catalysts are well known from the skilled person.
  • Typically, the catalyst may be used from 0.1% to 10% molar, preferably from 0.5% to 5% molar. Most preferably, the catalyst is used at 2% molar.
  • In one embodiment, the polymerization step is carried out at a temperature comprised between 60°C and 130°C, preferably between 80°C and 120°C.
  • In one embodiment, in the formula (I-5) above-mentioned, R2 is a methoxy group.
  • In the process of the invention, a preferred compound of formula (I-5) has the following formula (I-5-1):
    Figure imgb0057
     Rg and R'7 being a defined above.
  • In one embodiment, in formulae (I-5) and (I-5-1), R'7 is a (C1-C10)alkyl group, in particular a methyl group.
  • In one embodiment, in formulae (I-5) and (I-5-1), R'7 is a (C2-C6)alkenyl group, in particular a -CH2-CH=CH2 group.
  • In one embodiment, in formulae (I-5) and (I-5-1), Rg is a (C2-C6)alkenyl group, in particular a -CH2-CH=CH2 group or a -CH=CH2 group.
  • In one embodiment, in formulae (I-5) and (I-5-1), Rg is a -COORa group, in particular a -COO-(CH2)9-CH=CH2 group.
  • Preferred compounds of formula (I-5) are chosen from the group consisting of:
    Figure imgb0058
    Figure imgb0059
  • As used herein, the term "(Cx-Cy)alkyl" means a saturated aliphatic hydrocarbon group, which may be straight or branched, having x to y carbon atoms in the chain. Preferred alkyl groups have 1 to about 12, preferably 1 to 10, and more preferably 1 to 6, carbon atoms in the chain. The following alkyl groups may be cited as example: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl.
  • As used herein, the term "(Cx-Cy)alkylene" (or "alkylidene") refers to a divalent saturated aliphatic hydrocarbon radical, comprising from x to y carbon atoms, having preferably from 1 to 20, in particular 1 to 12 carbon atoms, and more preferably 2 to 10 carbon atoms. When said radical is linear, it may be represented by the formula (CH2)m wherein m is an integer varying from 1 to 12, and preferably from 2 to 10. The following alkylene may be cited as example: methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene.
  • As used herein, the term "(Cx-Cy)alkenyl" means an aliphatic hydrocarbon group containing a carbon-carbon double bond and which may be straight or branched having x to y carbon atoms in the chain. Preferred alkenyl groups have 2 to 12 carbon atoms in the chain; and more preferably about 2 to 10 or 2 to 6 carbon atoms in the chain. Exemplary alkenyl groups include for example ethenyl, propenyl, n-butenyl, i-butenyl, 3-methylbut-2-enyl, n-pentenyl, heptenyl, octenyl, nonenyl, decenyl.
  • As used herein, the term "alkenylene" means a hydrocarbon radical having at least one carbon-carbon double bond (straight chain or branched) wherein a hydrogen atom is removed from each of the terminal carbons such as ethenylene, propenylene, and the like.
  • As used herein, the term "(Cx-Cy)aryl" refers to an aromatic monocyclic or bicyclic hydrocarbon ring system having from x to y carbon atoms, preferably from 6 to 14, and more preferably 6 to 10, carbons atoms, wherein any ring atom capable of substitution may be substituted by a substituent. Examples of aryl moieties include, but are not limited to, phenyl, naphthyl, and anthracenyl.
  • As used herein, the term "arylene" refers to a radical derived from arene wherein two hydrogen atoms from the cycle have been deleted. Among the arylene radicals, the phenylene radical may be cited.
  • As used herein, the term "cycloalkyl" represents a non-aromatic monocyclic or bicyclic ring system having in particular from 3 to 12 carbon atoms. For example, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl may be cited.
  • As used herein, the term "cycloalkylene" refers to a divalent, saturated or partially unsaturated, non-aromatic monocyclic, bicyclic ring system having in particular from 3 to 12 carbon atoms, such as cyclobutylene, cyclopentylene, cyclohexylene.
  • As used herein, the term "heteroaryl" means a 5- to 14-, preferably a 5- to 10-, membered aromatic or partially saturated hetero mono- or bi-cyclic ring which consists of from 1 to 4 heteroatoms independently selected from the group consisting of sulfur atoms, oxygen atoms and nitrogen atoms including, but not limited to, pyrazolyl, furyl, thienyl, oxazolyl, tetrazolyl, thiazolyl, imidazolyl, thiadiazolyl, pyridyl, pyrimidinyl, pyrrolyl, thiophenyl, pyrazinyl, pyridazinyl, isooxazolyl, isothiazolyl, triazolyl, furazanyl, indolinyl, benzothienyl, benzofuranyl, benzoimidazolinyl, quinolinyl, tetrahydroquinolinyl, and the like.
  • As used herein, the term "hereroarylene" refers to a divalent heteroaryl as defined above.
  • As used herein, the term "alkoxy" means an alkyl-O- group wherein the alkyl group is as herein described. Exemplary alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy and heptoxy.
  • As used herein, the compounds of the invention such as those having one of the formulae (IV), (IV-bis), (VI), (XI-A) or (XI-B), may also be named 'polymers', especially as they comprise the repetition of n repetitive units.
  • The invention is described in the foregoing by way of non-limiting examples.
    • EXAMPLES Suppliers
  • Triazobycyclodecene, Zinc acetate, Dibutyltin oxide, Titanium butoxide, Grubbs 1st generation catalyst, Grubbs 2nd generation catalyst, Hoveyda Grubbs 1st generation catalyst, Hoveyda Grubbs 2nd generation catalyst, Succinic acid, Dimethyl succinate, Dimethyl terephthalate, 4,4'-methylenedianiline were purchased at Sigmal Aldrich. Sebacic acid and 1,6-diaminohexane were bought at Alfa Aesar. 2,5-furandicarboxylic acid, 1,1-diaminodecane and dimethylsebacate were supplied by TCI. Polarclean (methyl-5-(dimethylamino)-2-methyl-5-oxopentanoate) and Pripol were respectively supplied at Solvay and Croda. Maleic acid, terephtalic acid and Isophorone diamine were respectively purchased at Merck, Prolabo and Fisher.
    • Example 1: Preparation of polyesters (P1 to P8) by esterification General procedure
  • Diol (1 equivalent) and diester (or diacid) (1 equivalent) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 0.5 mol% of titanium butoxide
  • The following polymers were prepared according to this procedure:
    Figure imgb0060
    • P1 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.28 g of sebacid acid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%.
    • P2 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.75 g of Pripol (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow aid at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%.
    • P3 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.51 g of C22 diacid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%.
    • P4 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.16 g of succinic acid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%.
    • P5 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.16 g of maleic acid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%.
    • P6 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.23 g of terephtalic acid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%.
    • P7 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.18 g of 2,5-furandicarboxylic acid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200°C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide 0.5mol%. Table 1: Thermomechanical properties of polymers from methylated divanillyl diol and different diacids
    Diol Diacid Catalyst Tg (°C)a TD5% (°C)b Polymer
    Figure imgb0061
    Figure imgb0062
         		TiOBu4 0,5% 19 297 P1
    Figure imgb0063
         		-5 284 P2
    Figure imgb0064
         		13 260 P3
    Figure imgb0065
         		90 270 P4
    Figure imgb0066
         		97 240 P5
    Figure imgb0067
         		113 260 P6
    Figure imgb0068
         		140 260 P7
    a Tg (glass transition temperature) determined by DSC second heating cycle
    b TD5% (Temperature of 5% degradation) determined by TGA.
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70 °C to 200 °C at a rate of 10 °C.min-1. Consecutive cooling and second heating run were also performed at 10 °C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
  • Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10 °C.min-1 under air between 20 °C and 800 °C. TD5%= Temperature at which 5% of the material is degraded.
    • Example 2: Preparation of polyester P1 by transesterification General procedures
  • Methylated divanillic diol (1 equivalent) and dimethyl sebacate (1 equivalent) were stirred at 160 °C for 2 h under nitrogen flow and at 200 °C under vaccum for 6 h in the presence of 2 mol% of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol% of titanium butoxide.
  • According to another variant, methylated divanillic diol (1 equivalent) and dimethyl sebacate (1 equivalent) were stirred at 120 °C for 24 h in the presence of 10 mol% of TBD.
    • Polymers from methylated divanillyl diol and methyl sebacate (P1) using different catalysts (see table 2 below) • TBD10%
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.32 g of dimethyl sebacate (1,39 mmol) were stirred at 120°C for 24 h in the presence of 19.3 mg of TBD - 5%mol per ester function)
    • • TiOBu4 0.5%
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.32 g of dimethyl sebacate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • • TiOBu4 2%
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.32 g of dimethyl sebacate (1,39 mmol) were stirred at 160°C for 2 h under nitogen flow and at 200 °C under vacuum for 6h in the presence of 9.6 mg of Titanium butoxide (1mol% catalyst relative per ester function).
    • • ZnAc 2%
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.32 g of dimethyl sebacate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 6 mg of ZnAc (1mol% catalyst relative per ester function).
    • • DBTO 2%
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.32 g of dimethyl sebacate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 6.9 mg of DBTO (1mol% catalyst relative per ester function). Table 2: Properties of polymers from methylated divanillyl diol and methyl sebacate using different catalysts
    Diol Methylsebacate (diester) Catalyst (% by mol) Tg (°C)a TD5% (°C)c M n b (g/mol)b Ð
    Figure imgb0069
    Figure imgb0070
         		TBD 10% 14 299 33000 1.6
    TiOBu4 0,5% 34 319 65000 2.1
    TiOBu4 2% 36 301 30000 2
    ZnAc 2% 45 311 43000 1.8
    DBTO 2% 25 319 44000 1.9
    a determined by DSC second heating cycle
    b determined by SEC in DMF/DMSO 80/20
    c determined by TGA. (TD5%: Temperature of 5% degradation)
  • Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (Ð = M n/ M w) polystyrene (PS) standards.
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70 °C to 200 °C at a rate of 10 °C.min-1. Consecutive cooling and second heating run were also performed at 10 °C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
  • Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10 °C.min-1 under air between 20 °C and 800 °C. TD5%= Temperature of 5% degradation.
    • Example 3: Preparation of polyester P9 by transesterification General procedure
  • Methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 160 °C for 2 h under nitrogen flow and at 200 °C under vaccum for 6 h in the presence of 2 mol% of catalyst (titanium butoxide, zinc acetate or dibutyltin oxide) or in the presence of 0.5 mol% of titanium butoxide.
  • According to another variant, methylated dimethyl vanillate (1 equivalent) and 1,10-decanediol (1 equivalent) were stirred at 120 °C for 24 h in the presence of 10 mol% of TBD.
    Figure imgb0071
    • Polymers obtained from methylated dimethylvanillate and decanediol using different catalysts • TiOBu4 2%
  • 0.5 g methylated dimethyldivanillate (1,28 mmol) and 0.23 g of 1,10-decanediol (1,28 mmol) were stirred at 160°C for 2 h under nitrogen flow aid at 200 °C under vacuum for 6h in the presence of 8.7 mg of Titanium butoxide (1mol% catalyst relative per ester function).
    • • DBTO 2%
  • 0.5 g methylated dimethyldivanillate (1,28 mmol) and 0.23 g of 1,10-decanediol (1,28 mmol) were stirred at 160°C for 2 h under nitrogen flow aid at 200 °C under vacuum for 6h in the presence of 6.3 mg of DBTO (1mol% catalyst relative per ester function).
    • • TBD 10%
  • 0.5 g methylated dimethyldivanillate (1,28 mmol) and 0.23 g of 1,10-decanediol (1,28 mmol) (1,39 mmol) were stirred at 120°C for 24 h in the presence of 17.8 mg of TBD -5%mol per ester function)
    • • ZnAc 2%
  • 0.5 g methylated dimethyldivanillate (1,28 mmol) and 0.23 g of 1,10-decanediol (1,28 mmol) were stirred at 160°C for 2 h under nitrogen flow aid at 200 °C under vacuum for 6h in the presence of 4.7 mg of ZnAc (1mol% catalyst relative per ester function).
    • • TiOBu4 0.5%
  • 0.5 g methylated dimethyldivanillate (1,28 mmol) and 0.23 g of 1,10-decanediol (1,28 mmol) were stirred at 160°C for 2 h under nitrogen flow aid at 200 °C under vacuum for 6h in the presence of 2.2 mg of Titanium butoxide (0.25mol% catalyst relative per ester function). Table 3: Properties of polymers obtained from methylated dimethylvanillate and decanediol using different catalysts
    Methylated dimethyldivanilate Decanediol Catalyst (mol%) Tg (°C)a TD5% (°C)c M n (g/mol)b Ð
    Figure imgb0072
    Figure imgb0073
         		TiOBu4 2% 38 273 11000 1.3
    DBTO 2% 43 319 12000 1.6
    TBD 10% 36 253 3000 1.2
    ZnAc 2% 13 205 3000 1.0
    TiOBu4 0,5% 32 300 20000 1.7
    a determined by DSC second heating cycle
    b determined by SEC in DMF/DMSO 80/20
    c determined by TGA. Temperature of 5% degradation
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70 °C to 200 °C at a rate of 10 °C.min-1. Consecutive cooling and second heating run were also performed at 10 °C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
  • Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10 °C.min-1 under air between 20 °C and 800 °C. TD5%= Temperature of 5% degradation.
  • Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (Ð = M n/ M w) polystyrene (PS) standards.
    • Example 4: Preparation of polyester P'1 to P'8 by transesterification
  • The general procedure is identical to example 1.
  • The polymers P'1 to P'8 possess a structure similar to the one of polymers P1 to P8, except that the value of the repetitive units (n) differs, leading to polymers with various properties.
    • P'1 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.32 g of dimethyl sebacate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • P'2 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.79 g of Pripol ester (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • P'3 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.54 g of C22 diester (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • P'4 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.20 g of dimethyl succinate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • P'6 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.27 g of dimethyl terephtalate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • P'7 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.26 g of 2,5-furandicarboxylic acid (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence cf 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function).
    • P'8 synthesis
  • 0.5 g of methylated divanillyl diol (1,39 mmol) and 0.54 g of methylated dimethyldivanillate (1,39 mmol) were stirred at 160°C for 2 h under nitrogen flow and at 200 °C under vacuum for 6h in the presence of 2.4 mg of Titanium butoxide (0.25mol% catalyst relative per ester function). Table 4: Thermomechanical properties of polymers from of methylated divanillyl diol and different methyldiesters (with catalyst TiOBu4 0.5%)
    Diester Tg (°C) a TD5% (°C)c E' (GPa) b Polymers
    Figure imgb0074
         		5 308 2.0 P3'
    Figure imgb0075
         		101 310 2.0 P6'
    Figure imgb0076
         		68 302 5.1 P4'
    Figure imgb0077
         		-5 347 0.1 P2'
    Figure imgb0078
         		140 342 1.4 P7'
    Figure imgb0079
         		38 319 8.1 P1'
    Figure imgb0080
         		102 305 1.3 P8'
    a Determined by DSC second heating cycle
    b Determined by DMA 3 points flexion
    c Determined by TGA. Temperature of 5% degradation
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70 °C to 200 °C at a rate of 10 °C.min-1. Consecutive cooling and second heating run were also performed at 10 °C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
  • Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10 °C.min-1 under air between 20 °C and 800 °C. TD5%= Temperature of 5% degradation.
  • The mechanical properties were measured with a dynamic mechanical thermal analyzer DMA RSA 3 (TA instrument). The sample temperature was modulated from -80 °C to 220 °C, depending on the ample at a heating rate of 5 °C/min. The measurements were performed in a 3-point bending mode at a frequency of 1 Hz, an initial static force varying between 0.1 and 0.5 N and a strain sweep of 0.1 %.
    • Example 5: Preparation of polyamides P10 to P12 General procedure
  • Equimolar amount of diacids and diamines were dissolved in ethanol and the mixture was stirred slowly for 30 min at 80°C to alow the formation of ammonium salt. The salt was obtained as a fine powder after elimination of the solvent and dried under vacuum. The salt was warmed at 230°C for 4h.
  • The following polyamides were synthesized:
    Figure imgb0081
     Table 5: Thermomechanical properties of polyamides synthesized from methylated divanillic diacid and different diamines
    Diacid Diamine Tg (°C)a Name
    Figure imgb0082
    Figure imgb0083
         		124 P10
    Figure imgb0084
         		136 P11
    Figure imgb0085
         		157 P12
    a Determined by DSC second heating cycle
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70 °C to 200 °C at a rate of 10 °C.min-1. Consecutive cooling and second heating run were also performed at 10 °C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
    • Example 6: Preparation of epoxy resin synthesis General procedure
  • Bisepoxide and diamine were mixed together in ethanol. After evaporation of the solvent the mixture is poured into a matrix and warmed at 80°C for 4 h. Table 6: Thermomechanical properties of Epoxy resins
    Ratio Epoxy group /H of amine = 1
    Bisepoxy Diamine Tα (°C)a Tgb (°C) E' (GPa) 25°Cb TD5% (°C) TD30% (°C)
    Figure imgb0086
    Figure imgb0087
         		112 126 1.1 312 337
    a obtained from DMA
    b obtained from DSC
  • DMA RSA 3 (TA instrument). The sample temperature was modulated from -80°C to 220°C, depending on the sample at a heating rate of 5°C/min. The measurements were performed in a 3-point bending mode at a frequency of 1 Hz, an initial static force varying between 0.1 and 0.5 N and a strain sweep of 0.1%.
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70°C to 200°C at a rate of 10°C.min-1. Consecutive cooling and second heating run were also performed at 10°C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
  • Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10°C.min-1 under air between 20°C and 800°C. TD5%= Temperature of 5% degradation.
    • Example 7: Preparation of unsaturated polyesters General procedure
  • Unsaturated dimer (0.22 mmol) was dissolved in 1 mL of Polarclean. Grubbs catalyst (2% mol) was added to the flask. The flask was heated at 80°C under vacuum for 18h. Then 1 mL of ethyl vinyl ether was introduced to the flask to quench the reaction. The final polymer was diffolved into 1 mL of THF and reprecipitated in cold methanol.
  • The following polymers were synthesized:
    Figure imgb0088
     Table 7: Thermomechanical properties of polyesters by ADMET resins
    Monomer Catalyst M n (g/mol) Ð Tg (°C)a TD5% (°C) Polymer
    Figure imgb0089
         		HG1 7000 1.1 17 250 P14
    Figure imgb0090
         		HG2 40000 1.7 50.4 330 P15
    Figure imgb0091
         		HG2 29000 1.7 160 380 P16
    Figure imgb0092
         		HG2 10000 1.6 4.0 310 P17
  • The catalysts mentioned in table 7 are the following:
    Figure imgb0093
  • Differential Scanning Calorimetry (DSC) measurements were performed on DSC Q100 (TA Instruments). The sample was heated from -70°C to 200°C at a rate of 10°C.min-1. Consecutive cooling and second heating run were also performed at 10°C.min-1. The glass transition temperatures (Tg) were calculated from the second heating run.
  • Thermogravimetric analyses (TGA) were performed on TGA-Q50 system from TA instruments at a heating rate of 10°C.min-1 under air between 20°C and 800°C. TD5%= Temperature of 5% degradation.
  • Size exclusion chromatography (SEC) analysis was performed at room temperature in DMF/DMSO using simultaneous UV and refraction index detections. The elution times were converted to molar mass using a calibration curve based on low dispersity (Ð = M n/ M w) polystyrene (PS) standards.

Claims (15)

  1. The use of a compound having the following formula (I):
    Figure imgb0094
     wherein:
    - R1 is H or a OR7 group, R7 being H, a (C1-C10)alkyl group or a (C2-C6)alkenyl group;
    - R2 is a (C1-C6)alkoxy group;
    - R3 is H or a radical of formula (II)
    Figure imgb0095
     k being an integer varying from 1 to 6;
    - R4 is a (C1-C6)alkoxy group or a radical X chosen from the group consisting of: (C2-C6)alkenyl groups, (C1-C10)alkyl group, -COOH, -CH2OH, and -COORa, Ra being a (C1-C6)alkyl group or a (C2-C12)alkenyl group;
    and wherein:
    - when R1 is H, then R3 is a group of formula (II) and R4 is a (C1-C6)alkoxy group, and
    - when R1 is a OR7 group, then R3 is H and R4 is X as defined above,
    for the preparation of a polymer.
  2. A compound susceptible to be obtained by polymerization of the compound of formula (I) as defined in claim 1, and of a monomer chosen from the group consisting of: diacids, diesters, diamines, and epoxy compounds.
  3. A compound susceptible to be obtained by polymerization of the compound of formula (I) as defined in claim 1, comprising at least one repetitive unit U, wherein said unit U comprises a moiety having the following formula (III):
    Figure imgb0096
     wherein:
    - R1 represents OR7 group, R7 being H or a (C1-C10)alkyl group;
    - R2 represents a (C1-C6)alkoxy group.
  4. The compound of claim 2 or 3, having the following formula (IV):
    Figure imgb0097
     wherein:
    - A1 is chosen from the group consisting of:
    o a (C2-C10)alkylene radical;
    o a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group;
    o a (C2-C30)alkenylene radical;
    o an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;
    o a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group; and
    o a radical of formula -B1-B2-B3- wherein:
    • B2 is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, and
    • B1 and B3, identical or different, are chosen from the (C2-C15)alkylene radicals;
    o a radical of formula -B4-B5-, wherein B4 and B5, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with one or several substituents chosen from the (C1-C6)alkoxy groups;
    - R2 is a (C1-C6)alkoxy group;
    - R6 is (C1-C6)alkyl group; and
    - n is an integer varying from 1 to 130.
  5. A process for preparing a compound according to claim 4, comprising at least one step of polymerization of:
    - a compound having the following formula (I-1):
    Figure imgb0098
     wherein R2 and R6 are as defined in claim 4,
    - and a compound of formula (V) RbOOC-A1-COORb, wherein A1 is as defined in claim 4, and Rb is H or a (C1-C6)alkyl group.
  6. The process of claim 5, wherein the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu)4, dibutyl tin oxide (DBTO), and mixtures thereof.
  7. The compound of claim 2 or 3, having the following formula (IV-bis):
    Figure imgb0099
     wherein:
    - A4 is a (C2-C10)alkylene radical;
    - R2 is a (C1-C6)alkoxy group;
    - R6 is (C1-C6)alkyl group; and
    - n is an integer varying from 1 to 40.
  8. A process for preparing a compound according to claim 7, comprising at least one step of polymerization of:
    - a compound having the following formula (I-2):
    Figure imgb0100
     wherein R2 and R6 are as defined in claim 8,
    - and a compound of formula (VIII) :

             HO-A4-OH     (VIII)

    wherein A4 is as defined in claim 8.
  9. The process of claim 8, wherein the polymerization step is carried out in the presence of a catalyst chosen from the group consisting of: 5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), zinc acetate (ZnAc), Ti(OBu)4, dibutyl tin oxide (DBTO), and mixtures thereof.
  10. The compound of claim 2 or 3, having the following formula (VI):
    Figure imgb0101
     wherein:
    - A2 is chosen from the group consisting of:
    o a (C2-C10)alkylene radical;
    o a (C3-C12)cycloalkylene radical, optionally substituted by at least one (C1-C10)alkyl group;
    o a (C2-C30)alkenylene radical;
    o an arylene radical comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;
    o a heteroarylene radical comprising from 5 to 14 carbon atoms and at least one heteroatom chosen from O, S, and N, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group; and
    o a radical of formula -B'1-B'2-B'3- wherein:
    • B'2 is a (C1-C10)alkylene radical, and
    • B'1 and B'3, identical or different, are chosen from the arylene radicals comprising from 6 to 14 carbon atoms, optionally substituted in ortho, meta or para with a (C1-C10)alkyl group;
    - R2 is a (C1-C6)alkoxy group;
    - R6 is (C1-C6)alkyl group; and
    - n is an integer varying from 1 to 100.
  11. A process for preparing a compound according to claim 10, comprising at least one step of polymerization of:
    - a compound having the following formula (I-3):
    Figure imgb0102
     wherein R2 and R6 are as defined in claim 10,
    - and a diamine of formula (VII) H2N-A2-NH2, A2 being as defined in claim 10.
  12. A process for preparing a compound according to claim 2, comprising at least one step of polymerization of:
    - a compound having the following formula (I-4):
    Figure imgb0103
     wherein:
    . R2 is a (C1-C6)alkoxy group,
    . k is an integer varying from 1 to 6,
    . R' being a (C1-C6)alkoxy group;
    - and a diamine of formula (X) H2N-A3-NH2, A3 being a radical of formula -B"1-B"2- wherein:
    • B"1 is a (C3-C12)cycloalkylene radical, in which one or more carbon atom(s) is optionally substituted by at least one (C1-C10)alkyl group, and
    • B"2 is a (C1-C10)alkylene radical.
  13. The compound of claim 3, having the following formula (XI-A) or (XI-B):
    Figure imgb0104
     wherein:
    - R2 is a (C1-C6)alkoxy group;
    - R6 is a (C1-C10)alkyl group,
    - Y is chosen from the group consisting of: a bond, a (C1-C10)alkylene radical, a radical -C(O)O-Rc- and -Rc-O(O)C-, Rc being a (C1-C10)alkylene radical;
    - R8 is a (C1-C6)alkoxy group or a (C1-C10)alkyl group; and
    - n is an integer varying from 10 to 120.
  14. A process for preparing a compound according to claim 13, comprising at least one step of polymerization of a compound having the following formula (I-5):
    Figure imgb0105
     wherein:
    - R2 is as defined in claim 13;
    - R'7 is chosen from the group consisting of: (C1-C10)alkyl groups and (C2-C6)alkenyl groups, and
    - Rg is chosen from the group consisting of: (C1-C10)alkyl groups, (C2-C6)alkenyl groups, and -COORa groups, Ra being a (C2-C12)alkenyl group, wherein, when R7 is an alkyl group, then Rg is chosen from the (C2-C6)alkenyl groups and -COORa groups, and when R7 is an alkenyl group, then Rg is an alkyl group.
  15. The process of claim 14, wherein the polymerization step is carried out in the presence of a Grubbs catalyst.
EP14306563.9A 2014-10-03 2014-10-03 New phenolic polymers and preparation processes thereof Withdrawn EP3002303A1 (en)

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